Ceric hydrocarbyl silyloxides and process for their preparation

ABSTRACT

Ceric hydrocarbyl silyloxides are provided, as well as a process for preparing them, which comprises reacting ceric ammonium nitrate with a hydrocarbyl silanol, including a lower aliphatic silanol, under anhydrous conditions in the presence of an anhydrous base at a temperature within the range from about -30° C. to about 200° C. but preferably from 0° to about 150° C. until ceric hydrocarbyl silyloxide and the nitrate salt of the base are formed; the nitrates formed during the reaction can be separated from the reaction mixture and the ceric hydrocarbyl silyloxides isolated pure or as complexes with the solvent, or in some cases the ceric hydrocarbyl silyloxides can be used without separation from the reaction mixture in the presence of the nitrates.

This is a division of application Ser. No. 128,245, filed Dec. 3, 1987,U.S. Pat. No. 5,017,695.

Polyvalent metal alkoxides are an important class of versatileorganometallic compounds that have many industrial uses. In someinstances their uses parallel the metal carboxylates and otherorganometallic compounds, but they have advantages over such compoundsbecause of their catalytic properties, ease of hydrolysis, solubility inorganic solvents, and volatility. They have been used as paintadditives, water repellents, adhesion promoters, mordants, sizing agentsin enamel compositions, catalysts and also very importantly asintermediates in synthesis of other organic compounds.

There are four general preparative methods for metal alkoxides, allunder anhydrous conditions, as follows:

A. By reaction of the corresponding alcohol and metal, such as thealkali metals, alkaline earth metals, and aluminum, with the assistanceof an alkaline or acidic catalyst.

B. By reaction of the corresponding alcohol with the oxides andhydroxides of the metal, for instance NaOH or Na₂ O, V₂ O₅ and MoO₃.SH₂O.

C. By reaction of the corresponding alcohol and metal halide in thepresence of an anhydrous base. A typical example is the preparation ofTh(OR)₄ or Zr(OR)₁₄ :

    ThCl.sub.4.4ROH+4NaOR→Th(OR).sub.4 +4NaCl

    ZrCl.sub.4 +4ROH+4NH.sub.3 →Zr(OR).sub.4 +NH.sub.4 Cl

The reaction can be used for preparing alkoxides of titanium, hafnium,germanium, niobium, tantalum, aluminum and tin.

D. By transetherification of the metal alkoxides of lower alcohols, suchas the methoxides, ethoxides or isopropoxides, with a higher alcohol.

Method A is exemplified for a number of yttrium, lanthanum and otherlanthanide alkoxides by L. Brown and K. Mazdiyasni in InorganicChemistry, (1970) 2783. The reaction, previously thought to be usefulonly for the alkali metals, magnesium and aluminum, was extended by themto the synthesis of yttrium and all of the lanthanide isopropoxides. Forthe lower lanthanides, such as lanthanum, cerium, praesodymium andneodymium, a mixture of HgCl₂ and Hg(C₂ H₃ O₂)₂ or HgI₂ is used as acatalyst, to increase both the rate of reaction and percent yield.Generally, 5 g of metal turnings is reacted with about 300 ml ofisopropyl alcohol at reflux temperature for about 24 hours and in thepresence of a small amount of Hg salt catalyst. The yields are said tobe 75% or better.

Most of the other examples in the literature of the pre preparation ofalkoxides of lanthanides refer to the use of the corresponding metalhalides. In some cases, a complex LaCl₃.3ROH is preferred to the LaCl₃(Misra et al, Austr. J. Chem 21 797 (1978) and Mehrotra and Batwara,Inorganic Chem 9 2505 (1970)).

An interesting variation of Method D is mentioned by Tripathi, Batwara,and Mehrotra J. C. S. A. 1967 991. Lower ytterbium alkoxides (such asthe methoxide and ethoxide) were synthesized from ytterbiumisopropoxide, by transetherification with methanol or ethanol. Owing totheir sparing solubility, these alcohols were removed by precipitationas the reaction proceeded, driving the transetherification tocompletion.

In general, Methods A, B and C are only suited for preparation of thelower alkoxides, such as the methoxides, ethoxides and isopropoxides,since the reactivity of higher alcohols diminishes with increase intheir molecular weights. The higher alkoxides are better prepared byMethod D, which is a two-step process.

The only published method for preparing ceric alkoxides applied Method Cto ceric chloride, Bradley et al, J. C. S. 1956 2260-64. Since ceriumtetrachloride is unstable, the dipyridinium cerium hexachloride complexwas Bradley et al's choice as starting material.

Cerium dioxide was first converted to ceric ammonium sulphate. Pureceric hydroxide was precipitated from an aqueous solution of cericammonium sulphate and washed thoroughly. The freshly-prepared cerichydroxide, suspended in absolute alcohol, was treated with anhydroushydrogen chloride and then pyridine was added, which formed theinsoluble dipyridinium cerium hexachloride complex (Py)₂ CeCl₆. Thecomplex was filtered, dried, and used for preparing the methoxide,ethoxide and isopropoxide directly, while the propyl, butyl, secondarybutyl, neopentyl and n-pentyl alkoxides were made by alcoholinterchange, i.e., transetherification, from the isopropoxide. Themethoxide and ethoxide were also made by exchange from the isopropoxide.

Gradeff and Schreiber, U.S. Pat. Nos. 4,489,000, patented Dec. 18, 1984and 4,663,439, patented May 5, 1987 provide a process for preparingceric alkoxides which comprises reacting ceric ammonium nitrate with analcohol under anhydrous conditions in the presence of an anhydrous baseat a temperature within the range from about -30° C. to about 200° C.,preferably from about 0° C. to about 150° C., until ceric alkoxide andthe nitrate salt of the base are formed.

This process avoids the necessity described by Bradley et al of firstpreparing the ceric hydroxide from the ceric salt, in their case, cericammonium sulphate, and converting the hydroxide subsequently to thechloride, which needs to be stabilized as the pyridine complex.

It is rather surprising, despite the considerable volume of work done onthe preparation of rare earth metal silicon compounds, that ceriumhydrocarbyl silyloxides are unknown, as well as a suitable process forpreparing them.

Bradley and Thomas, J. Chem. Soc. 1959 3404 have reported work on alkylsilyloxy derivatives of titanium, zirconium, neobium and tantalum, usingtrimethyl silanolysis of titanium or zirconium isopropoxides, or usingtrialkyl silyl acetate in place of the silanol, but there is noreference to cerium.

Bradley and Prevedorou-Demas, J. Chem. Soc. 1964 1580 reported furtherwork on zirconium oxide trimethyl silyloxide polymers.

In neither paper is there reference to cerium silyloxides.

In accordance with the present invention, a process is provided forpreparing ceric hydrocarbyl silyloxides which comprises reacting cericammonium nitrate with a silanol under anhydrous conditions in thepresence of an anhydrous base at a temperature within the range fromabout -30° C. to about 200° C., preferably from about 0° C. to about150° C., until ceric hydrocarbyl silyloxide and the nitrate salt of thebase are formed.

This process is direct and economical, and in addition utilizes cericammonium nitrate, a commercially available material that is relativelyinexpensive.

The product, a ceric hydrocarbyl silyloxide, is believed to be novel,since it has not previously been reported in the literature, and ischaracterized by one or more groups having a tetravalent cerium linkedvia oxygen to one, two, three or four silicon atoms, as shown, theremaining three or two, respectively, valences of the silicon beinglinked to hydrocarbyl groups having from one to about ten carbon atoms.The compounds can have one, two, three or four silicon atoms, in asingle unit, or in a plurality of such units linked in linear, branchedor cage-type oligomers or polymers, when the starting silanol is a diol.

In addition, if desired, a ceric hydrocarbyl silyloxide nitrate, isformed when the amount of silanol is less than the stoichiometric amountrequired to react with all of the valence positions of the cerium, andcan be isolated from the reaction mixture. These free valence positionsof the cerium thus carry NO₃ groups instead of silyloxide groups.

A ceric hydrocarbyloxy hydrocarbyl silyloxide can be formed bytransetherifying a ceric hydrocarbyl oxide with silanol and by employingan amount of silanol that is less than the stoichiometric amountrequired to react with all of the valence positions of the cerium, sothat only part of the hydrocarbyloxy groups are displaced by silyloxidegroups. These valence positions of the cerium thus carry hydrocarbyloxygroups.

Accordingly, to prepare a ceric hydrocarbyloxy hydrocarbyl silyloxide, aceric alkoxide is transetherified with the silanol having the desiredhydrocarbyl group and the desired number of hydroxyl groups underanhydrous conditions at a temperature within the range from about -30°C. to about 200° C., thereby displacing part of the aliphatic alcohol ofthe alkoxide and forming the ceric hydrocarbyloxy hydrocarbyl silyloxideof the silanol. The ceric hydrocarbyloxy hydrocarbyl silyloxide ifinsoluble in the reaction mixture precipitates out in the course of thetransetherification.

Accordingly, the ceric hydrocarbyl silyloxides can be defined by thefollowing general formula: ##STR1## where OX₁, OX₂, OX₃ and OX₄ areselected from the group consisting of OR₁, NO₃ and [O]_(4-y) SiR_(y) ;and any two of X₁ and X₂ and X₃ and X₄ can be taken together as >SiR_(y); the number of SiR_(y) can be 1, 2, 3 or 4 and y can be 1, 2 or 3.

When y=2, the silicon is linked to two of the oxygens as >SiR_(y) in (1)the same or (2) a different cerium atom; in (1) the species aremonomeric; in (2) they can be oligomers or polymers.

At least one of X₁, X₂, X₃ and X₄ is O_(4-y) SiR_(y), at least one R ishydrocarbyl, and no more than one R may be hydrogen.

Examples of compounds falling within Formula I according to the value ofX₁, X₂, X₃, X₄ include: ##STR2## wherein y is the number of cerium atomsin the polymer and can range from 1 to about 10. ##STR3## wherein m₁ isthe number of such units in the polymer and can range from 1 to about10.

R in the above formulae is hydrogen or a hydrocarbyl group having fromone to about ten carbon atoms, and the R's attached to any silicon canbe the same or different.

R₁ is a hydrocarbyl group attached via oxygen to cerium and having fromone to about ten carbon atoms, and the R₁ 's attached to any cerium canbe the same or different.

Exemplary hydrocarbyl R and R₁ groups include alkyl, straight orbranched alkenyl, cycloalkyl, cycloalkenyl, phenyl and alkyl phenyl,naphthyl and alkyl naphthyl groups.

Exemplary R and R₁ alkyl include methyl, ethyl, propyl, isopropyl,butyl, sec-butyl, hexyl, octyl, isooctyl, 2-ethylhexyl, nonyl and decyl.

Exemplary R and R₁ alkenyl include vinyl, allyl, butenyl, hexenyl,octenyl, nonenyl and decenyl.

Exemplary R and R₁ cycloalkyl include cyclopentyl, cyclohexyl,cycloheptyl and cyclooctyl; cyclopentenyl, cyclohexenyl andcycloheptenyl.

Exemplary R and R₁ alkaryl include phenyl, phenylmethyl, andphenylethyl.

The hydrocarbyl silanol can be any of several types: ##STR4## wherein n₁is the number of such units in the polymer and can range from 1 to about10.

Group (d) includes solid silicone resins containing free OH groups,which can be solubilized and used in the reaction with ceric ammoniumnitrate to form silicone resin linked to cerium via the oxygen.

R is hydrogen or the hydrocarbyl group desired in the silyloxideproduct, and the R's attached to an silicon can be the same ordifferent.

Preferred subclasses of silanols include: ##STR5##

The process proceeds with ease with the lower aliphatic monohydric,dihydric and trihydric silanols having one, two or three hydrocarbylgroups of from one to six carbon atoms, for example, trimethyl silanol,triethyl silanol, tripropyl silanol, triisopropyl silanol, tributylsilanol, triisobutyl silanol, tri-sec-butyl silanol, tri-tert-butylsilanol, tripentyl silanol, triisopentyl silanol, tri-sec-pentylsilanol, tri-tert-pentyl silanol, and trihexyl silanol; dimethylsilanediol, diethyl silanediol, dipropyl silanediol, diisopropylsilanediol, dibutyl silanediol, diisobutyl silanediol, di-sec-butylsilanediol, di-tert-butyl silanediol, dipentyl silanediol, diisopentylsilanediol, di-sec-pentyl silanediol, di-tert-pentyl silanediol anddihexyl silanediol; methyl silanetriol, ethyl silanetriol, propylsilanetriol, isopropyl silanetriol, butyl silanetriol, isobutylsilanetriol, sec-butyl silanetriol, tert-butyl silanetriol, pentylsilanetriol, isopentyl silanetriol, sec-pentyl silanetriol, tert-pentylsilanetriol and hexyl silanetriol.

A higher aliphatic, cycloaliphatic or aromatic hydrocarbyl silanolhaving hydrocarbyl groups of at least seven up to about ten carbon atomscan be incorporated directly in the reaction mixture together with alower aliphatic silanol having hydrocarbyl groups of from one to sixcarbon atoms to form a ceric silyloxide of the higher silanol. Exemplaryare triheptyl silanol, triisoheptyl silanol, trioctyl silanol,triisooctyl silanol, tri-2-ethyl-hexyl silanol, tri-sec-octyl silanol,tri-tert-octyl silanol, trinonyl silanol, triisonoyl silanol, tridecylsilanol, tricyclopropyl silanol, tricyclobutyl silanol, tricyclopentylsilanol, tricyclohexyl silanol, tricycloheptyl silanol, tricyclooctylsilanol, tripropyl cyclohexyl silanol, trimethyl cyclohexyl silanol andtrimethyl cycloheptyl silanol, triphenyl silanol, tribenzyl silanol,triphenethyl silanol, and triphenpropyl silanol, diheptyl silanediol,diisoheptyl silanediol, dioctyl silanediol, diisooctyl silanediol,di-2-ethylhexyl silanediol, di-sec-octyl silanediol, di-tert-octylsilanediol, dinonyl silanediol, diisononyl silanediol, didecylsilanediol, dicyclopropyl silanediol, dicyclobutyl silanediol,dicyclopentyl silanediol, dicyclohexyl silanediol, dicycloheptylsilanediol, dicyclooctyl silanediol, dipropyl cyclohexyl silanediol,dimethyl cyclohexyl silanediol and dimethyl cycloheptyl silanediol;diphenyl silanediol, dibenzyl silanediol, diphenethyl silanediol,diphenpropyl silanediol; heptyl silanetriol, isoheptyl silanetriol,octyl silanetriol, isooctyl silanetriol, 2-ethyl-hexyl silanetriol,sec-octyl silanetriol, tert-octyl silanetriol, nonyl silanetriol,isononyl silanetriol, decyl silanetriol, cyclopropyl silanetriol,cyclobutyl silanetriol, cyclopentyl silanetriol, cyclohexyl silanetriol,cycloheptyl silanetriol, cyclooctyl silanetriol, propyl cyclohexylsilanetriol, methyl cyclohexyl silanetriol and methyl cycloheptylsilanetriol; phenyl silanetriol, benzyl silanetriol, phenethylsilanetriol, phenpropyl silanetriol, napthyl silanetriol (where toounstable, the triols are used in the form of their ethers).

The final reaction product is the ceric hydrocarbyl silyloxide of thehigher silanol, but it is believed that the lower silanol expedites thereaction by first forming a silyloxide with the cerium, this silyloxidebeing converted by transetherification with the higher silanol to thesilyloxide of the higher silanol.

The above-described reactions can be carried out in the presence of anexcess of the silanol, which also can be a solvent for the correspondingsilyloxide. Inert solvents in addition to the reactant silanol may beneeded in order to dissolve the ceric ammonium nitrate such as DME, orother glymers, THF or alcohols. Inert solvents also may be required toseparate products from the nitrate by-products, for instance, pentane,benzene, toluene, pet. spirits etc. If desired, the solvent can beseparated from the reaction product by distillation at atmospheric orreduced pressure, following completion of the reaction. It is understoodthat one or two molecules of a solvent such as DME for instance mayremain coordinated to the cerium.

The reaction proceeds under anhydrous conditions at a temperature withinthe range from about -30° C. to about 200° C., preferably from about 0°C. to about 50° C., most preferably at room temperature, depending onthe solvent system and base used.

The case where ceric ammonium nitrate is totally or partially dissolvedin an alcohol such as methanol, ethanol or isopropanol, or where thesilanol is mixed with an alcohol and then added to the ceric ammoniumnitrate, is a special one that may involve going "in situ" via thealkoxide of cerium corresponding to the alcohol present. In some ofthese cases the reaction may take longer to complete and may requireheating. In each, however, the product is the desired cerium silyloxide.

The reaction of the ceric ammonium nitrate proceeds in the presence of asuitable anhydrous base, such as ammonia, or an alkali metal reactedfirst with the silanol to produce the corresponding alkali metalsilanolate which is then reacted with the ceric ammonium nitrate. Abyproduct of the reaction is the corresponding ammonium or alkali metalnitrate salt.

The reaction time is not critical. The reaction is continued until thedesired silyloxide product is formed. This may take from ten minutes toseveral hours, but it is not necessary to carry the reaction beyond afive hour reaction time. Usually, reaction is complete within from oneto three hours.

The reaction can proceed quite rapidly at room temperature, and if itdoes, it very likely will also proceed at temperatures well below roomtemperature, down to -30° C., but there is no reason to incur theadditional expense of cooling the reaction mixture. The upper limit onreaction temperature is imposed by the volatility of the reactionmixture or any component thereof, and their decomposition temperature.There is no reason to use a temperature above the boiling point of thereaction mixture at atmospheric pressure, but if the boiling temperatureis too low, as, for example, in the case of methanol, a closed reactionvessel or pressurized system can be used. The reaction temperature neednot exceed 200° C., taking the above factors into consideration.

The amount of anhydrous base is stoichiometric, since the function ofthe base cation, ammonia or alkali metal, is to take up nitrate from theceric ammonium nitrate starting material. An excess can be used, but isunnecessary.

The amount of silanol is at least from 1 to 6 moles per mole of cericammonium nitrate, but larger amounts can also be used. Larger thanstoichiometric amounts will be used, of course, when the silanol is alsoto function as a solvent, according to the dilution of the reactionmixture required.

The reaction mixture contains the nitrate salt of the base cation, andthis can be separated from the silyloxide during work-up. If this saltis less soluble in the reaction mixture than the silyloxide reactionproduct, it can be filtered off, and thereby separated from the reactionproduct. Alternatively, the reaction mixture can be taken up in an inertsolvent such as benzene, DME, THF, toluene or hexane, preferably aninert solvent in which the silyloxide reaction product is soluble, andthe nitrate or salt insoluble, whereupon the nitrate salt is filteredoff or centrifuged out.

Depending on reaction and work-up conditions, the silyloxide can beisolated as associations with one or more molecules of alcohol or asolvent.

For some applications the cerium silyloxides can be used in the form inwhich they exist in the reaction mixture at the end of the reaction,without actually isolating them from the reaction mixture, or separatingthem from the nitrates, which saves processing and handling costs.

The following Examples in the opinion of the inventors representpreferred embodiments of the invention:

EXAMPLE 1 Preparation of Cerium (IV) tetra(triphenyl silyloxide)##STR6##

4 g (0.00729 m) of ceric ammonium nitrate was suspended in 40 ml (35 g)dimethoxy ethane. Upon adding 8 g (0.0291 m) of triphenylsilanol as asolid an almost clear orange solution was formed. In the next fiveminutes NH₃ gas was bubbled through the solution, causing an exothermicreaction (cooling was not necessary) along with immediate formation of awhite precipitate. After stirring for an additional 10 minutes, theprecipitate was isolated by using a frit filter. Subsequent evaporationof the obtained yellow filtrate to dryness resulted in an oily product,which however, became powdery upon further drying under vacuum (1 torr).The final product was a white powder, fairly air stable, yield: 8.5 g(94%).

Solubility: good in toluene; soluble in DME; moderately soluble inacetone; insoluble in n-hexane and acetone.

NMR results: ¹ H CHCl₃ -d δ3.15; 3.35; 7.06; 7.14; 7.18; 7.26; 7.53;7.61. ¹³ C CHCl₃ -d δ59.83; 71.79; 127.49; 129.17; 135.13; 137.57.

EXAMPLE 2 Preparation of Cerium (IV) bis(1, 1-diphenyl silyloxide)##STR7##

To a stirred suspension of 5 g (0.00912 mole) of (NH₄)₂ Ce(NO₃)₆ in 40ml (35 g) dimethoxy ethane, 3.94 g (0.0182 m) of Ph₂ Si(OH)₂ was addedas a solid, forming an almost clear red/orange solution. The bubbling ofNH₃ gas through the solution caused an exothermic reaction, and theimmediate formation of a white precipitate, while the (NH₄)₂ Ce(NO₃)₆was used up in a few minutes. After 10 minutes of stirring the reactionwas regarded as complete, and subsequent filtration and removal of thesolvent yielded 4.5 g (86%) of an orange/yellow powder.

Solubility: soluble in CH₃ CN, DME, toluene, acetone; insoluble inn-hexane.

NMR results: ¹ H (THF-d₈) δ3.31; 3.48; 7.21; 7.66; 7.75. ¹³ C(THF-d₈)δ58.84; 72.6; 128.02; 129.59; 135.33; 139.23.

EXAMPLE 3 Reaction of (NH₄)₂ Ce(NO₃)₆ with 1Ph₂ Si(OH)₂ ##STR8##

Following the same procedure as in Example 2, to 5 g (0.00912 m) (NH₄)₂Ce(NO₃) in 40 ml (35 g) dimethoxy ethane 2 g Ph₂ Si(OH)₂ (0.00924 m) wasadded as a solid. The reaction was complete after 10 minutes.

Yield: 3.5 g (85.2%) of an orange powder.

Solubility: soluble in CH₃ CN, acetone, DME to form foggy solutions;insoluble in hexane and toluene.

¹ H and ¹³ C N-MR data are identical with those of Example 2.

EXAMPLE 4 Preparation of Cerium (IV) tetra(triethyl silyloxide) ##STR9##

To the stirred suspension of 10.36 g (0.0189 mole) of (NH₄)₂ Ce(NO₃)₆ in50 ml (43 g) dimethoxy ethane, 10 g (0.0751 m) of triethyl silanol wasadded via a syringe. In the next ten minutes NH₃ gas was bubbled slowlythrough the orange/yellow solution, causing the immediate formation of awhite precipitate. After stirring for additional 30 minutes, the mixturewas filtered using a frit filter and the obtained yellow/green filtratewas evaporated to dryness. However, it was not possible to convert theobtained heavy yellow oil into a powder after several treatments undervacuum.

Yield of (NH₄)NO₃ recovered: 8.7 g (theory; according to the abovereaction equation: 9 g)

NMR results: ¹ H(C₆ H₆ -d₆) δ0.62(t); 1.00 (q) ¹³ C(C₆ H₆ -d₆) 6.94;7.12. ²⁹ Si(C₆ H₆ -d₆) δ15.14.

EXAMPLE 5 Preparation of Cerium (IV) bis(1,1-diphenyl silyloxide)##STR10##

To a stirred suspension of 3.4 g (0.02179 mole) ofdilithiodiphenyldisilanolate in 30 ml (26 g) 5.97 g (0.0108 m) of DME(NH₄)₂ Ce(NO₃)₆ was added as a solid. After 2 hrs of stirring a whiteprecipitate and a dark red/brown solution had been formed. No unreacted(NH₄)₂ Ce(NO₃)₆ was left. Subsequent evaporation of the solvent causedthe formation of a dark red heavy oil. After keeping the oil for 10hours at oil pump vacuum it was possible to convert it into a sticky,wet orange powder.

NMR results: ¹ H(CHCl₃ -d) δ3.34; 3.51; 7.22; 7.30; 7.37; 7.52. ¹³C(CHCl₃ -d) δ59.39; 71.74; 127.71; 130.04; 134.26.

EXAMPLE 6 Preparation of Cerium (IV) tetra(trimethyl silyloxide)##STR11##

10.68 g (0.01948 m) (NH₄)₂ Ce(NO₃)₆ and 15 g (0.1169 m) of potassiumtrimethyl silanolate were put together in a 200 ml flask. Upon adding of40 ml of tetrahydrofuran, the mixture was stirred 8 hrs, after whichtime a greenish yellow precipitate had been formed. Upon filtration viaa frit filter 45 ml of a clear colorless solvent mixture (THF+Me₃ SiOH)and 16.5 g of a greenish/yellow powder [Ce(OSiMe₃)₄ +NH₄ NO₃ ] (theory:17.5 g) was obtained. The powder was washed with 250 ml of distilledwater in air, to yield 4.2 g of a light yellow powder (=43%).

The product was a fairly air stable, in organic solvents insoluble finepowder. It is apparently not attacked by H₂ O.

EXAMPLE 7 Preparation of Cerium (IV) tetra(trimethyl siloxane) (NH₄)₂Ce(NO₃)₆ +6Me₃ SiOH+NH₃ →Ce(OSiMe₃)₄ +6NH₄ NO₃ +2Me₃ SiOH

10.2 g of ceric ammonium nitrate (0.0186 m) was suspended in 20 ml (17g) of DME and stirred for 10 minutes. 12.3 ml (=10.05 g=0.1116 m) oftrimethylsilanol were added via a syringe. As Me₃ SiOH was not solublein the red suspension of the cerium complex two layers have been formed.Under vigorous stirring NH₃ gas was bubbled through the solutionaccompanied by the formation of a bright yellow precipitate which turnedto a pale yellow on further reaction with NH₃ gas. In the first 15minutes the reaction proceeded very exothermically; however, after 1/2hour the reaction temperature decreased. 40 ml of diethylether was addedto maintain stirring.

Afterwards, the product was filtered and washed with 3×40 ml of ether.After drying at oil pump vacuum 12.1 g of a pale yellow powder wasobtained. The product mixture containing NH₄ NO₃ was washed 200 ml of H₂O. The remaining solid was dried at vacuum and 5.4 g of a light yellowpowder was obtained (58.5%).

The product is not soluble in any common solvents.

EXAMPLE 8 Preparation of Cerium (IV) tetra(triphenyl silyloxide)##STR12##

3.9 g (0.013 m) of sodium triphenylsilanolate was dissolved in 30 ml ofDME (26 g). This solution was dropped into the red clear solution of1.19 g (0.00217 m) (NH₄)₂ Ce(NO₃)₆ in 15 ml (13 g) of DME. A yellowishwhite precipitate was formed immediately along with NH₃ gas, as wasindicated by pH paper. After stirring the mixture overnight the solventwas evaporated at 40° C. to yield 4.94 g (theory 5.0 g) of a lightyellow powder. The crude product was washed with two portions of each 30ml iso-propanol in order to remove Ph₃ SiOH. The remaining residue wasextracted with 45 ml of benzene to give a clear yellow filtrate. Uponremoving the solvent in vacuum, 2.6 g (96%) of a white powder wasobtained.

Soluble in CHCl₃, DME, THF, C₆ H₆.

¹ H and ¹³ C NMR data are identical with those of Example 1.

EXAMPLE 9 Preparation of Cerium (IV) tetra(triphenyl silyloxide)##STR13##

3.37 g (0.02173 m) of sodium triethylsilonate was prepared by reacting0.5 g Na with 2.87 g Et₃ SiOH in 30 ml (26 g) DME during 12 hours. Tothe clear colorless solution 1.98 g (0.0036 m) of (NH₄)₂ Ce(NO₃)₆ (in 20ml, 17 g DME) was added. A white precipitate was formed immediatelyalong with NH₃ gas. After a reaction time of ˜1 hour all of the (NH₄)₂Ce(NO₃)₆ had reacted. Following filtration the yellow filtrate wasevaporated to dryness to yield a yellow oily product.

¹ H and ¹³ C NMR data are identical with those of Example 4.

EXAMPLE 10 Preparation of Cerium (IV) bis(1,1-diphenyl silyloxide)##STR14##

To the clear light yellow solution of 1.92 g (0.0084 m) Ph₂ Si(OLi)₂ in30 ml (24 g) methanol, was dropped the clear red solution of 1.53 g(NH₄)₂ Ce(NO₃)₆ in 10 ml MeOH. A pale yellow precipitate was formedimmediately along with NH₃ gas as was indicated by pH paper. Afterstirring for three hours the reaction mixture was filtered using aSchlenk frit; subsequent evaporation of the pale yellow filtrate todryness yielded a pale yellow powder.

¹ H and ¹³ C NMR data are identical with those of Example 2, except thatthe product from methanol as solvent contains two coordinated MeOHmolecules.

EXAMPLE 11 Preparation of Cerium (IV)diisopropoxy-1,1-diphenylsilanediolate ##STR15##

To the clear yellow solution of 6 g (0.01238 mole) Ce(OisoC₃H.sub.η)₄.1.8 isoC₃ H.sub.η OH in 30 ml (26 g) DME, 2.67 g (0.01238 m)of ##STR16## diphenylsilanediol was added as a solid. After a fewminutes of stirring a thick suspension had been formed, by adding of ˜10ml of DME a clear solution was obtained, which was stirred for threehours. The solvent was removed with mild heating (˜40° C.) under oilpump vacuum. Before complete drying the solid foamed up, but could beeasily converted into a powder by using a spatula.

Yield: 5 g (85.5%) of a yellow, slighly air sensitive powder. Verysoluble in CHCl₃, ether, DME, soluble in C₆ H₆, not soluble in CH₃ CN.m.p. 95°-100° C.

NMR results: ¹ H(CHCl₃ -d) δ1.26; 1.33; 5.1; 7.26; 7.72. ¹³ C(CHCl₃ -d)δ27.75; 127.27; 128; 129; 134.85.

Elemental analyses: Calcd for C₁₈ H₂₄ O₄ SiCe 472.205 ##STR17## 472.205C 45.74(39.20); H 5.08(4.93); Si 5.94(6.04); Ce 29.64(30.60). Calcd forC₁₅ H₂₆ O₅ SiCe: 454.205 ##STR18## C 39.63; H 5.72; Si 6.18; Ce 30.84 in() values found.

The yield of 85.5% has been based on the M.W. 472.205.

EXAMPLE 12 Preparation of Cerium (IV)bis(iso-propoxide)-bis(trimethylsiloxane) Ce(O-isoC₃ H.sub.η)₄.1.8 isoC₃H.sub.η OH+2(CH₃)₃ SiOH→(isoC₃ H.sub.η O)₂ Ce(OSi(CH₃)₃)₂ +3.8 isoC₃H.sub.η OH

10.2 g (0.021 m) of ceric isopropoxide was dissolved in 20 ml (17 g) ofDME. To the stirred solution 4.65 ml (=3.79 g=0.042 m) oftrimethylsilanol was added via a syringe. After each 30 minutes the redsolution turned foggy and gradually a fine precipitate began to form.The mixture was allowed to react in the next four hours. Subsequentfiltration via a Schlenk frit and drying at oil pump vacuum yielded 3.1g of a pale yellow powder (33.8%).

NMR data: ¹ H (C₆ H₆ -d₆) δ0.3356; 1.34; 1.41; 4.30. ¹³ C (C₆ H₆ -d₆)δ3.73; 26.37; 71.98.

EXAMPLE 13 Preparation of Cerium (IV) tetramethylsiloxydiolate-di-isopropoxide ##STR19##

13.74 g (0.0314 m) of ceric isopropoxide and 5.25 g (0.0314 m) oftetramethyl disiloxanol were dissolved in each 10 ml of DME. Upon addingthe Si-compound to the Ce-complex solution a yellow precipitate wasimmediately formed which partially went into solution. However, by fastfiltration and drying at vacuum, it was possible to recover Ca 100 mg ofyellow precipitate.

NMR data: ¹ H(CHCl₃ -d) δ0.0197; 1.26; 4.71. ¹³ C(CHCl₃ -d) δ0.9941;27.05; 71.80.

After the filtration a clear red filtrate was obtained which on removingthe solvent turned into a heavy oil. It was not possible to convert itinto a powder by further drying. Its NMR data are almost identical withthose of the above mentioned yellow precipitate.

The cerium hydrocarbyl silyloxides can be employed in the manufacture ofoxide powders containing cerium and silicon, useful in preparing highperformance ceramics; hard gels and films containing cerium and silicon;optical fibers containing cerium and silicon polymers or oxides;additives for biocides, additives for silicone coatings such as paints,treatment of textiles and other cellulosic materials. They can also beused in various catalytic applications as for instance curing ofsilicone rubber, and catalysts in the manufacture of polyurethaneproducts. The Table illustrates the potentials of some of the newcompounds in a standard test demonstrating and comparing catalyticactivity:

    ______________________________________                                                       Concentration                                                                             Solidification Time                                Compound Tested                                                                              ppm         min.                                               ______________________________________                                        Nickel acetyl acetonate                                                                      314         115                                                (a standard)                                                                  Ce(O.sub.2 SiPh.sub.2).sub.2                                                                 260         105                                                (PrO).sub.2 Ce--(O.sub.2 SiPh.sub.2)                                                         320         105                                                (PrO).sub.2 Ce--(OSiMe.sub.3).sub.2                                                          372          45                                                Ce(OSiEt.sub.3).sub.4                                                                        233          80                                                Ce(OSiMe.sub.3).sub.4                                                                        282          69                                                ______________________________________                                    

The reactions were run with polyoxypropylene triol (Union Carbide's NiAXTriol LG-56) and toluene diisocyanate in a procedure described inJournal of Applied Polymer Science, Vol IV, No. 1, pp 207-211 (1960).

Some of the new products are surprisingly resistant to hydrolysis, whileothers hydrolyze very slowly. Thus it is possible to form a silyloxidehaving any desired rate of hydrolysis, according to the application.

Furthermore, having silicon and cerium present together in the samemolecule is advantageous when both are required, as compared to addingseparate cerium and silicon alkoxides.

The term "ceric hydrocarbyl silyloxide" as used in this specificationand in the claims generically encompasses any compound having ceriumattached via oxygen to silicon of a silyloxide group, and also includesspecifically such compounds containing, in addition nitrate groupsand/or hydrocarbyloxy groups attached to cerium.

Having reagard to the foregoing disclosure the following is claimed asinventive and patentable embodiments thereof:
 1. A ceric hydrocarbylsilyloxide characterized by at least one group having a tetravalentcerium atom linked via oxygen to one, two, three or four silicon atoms,the remaining valences of the silicon being linked to hydrocarbyl groupshaving from one to about ten carbon atoms.
 2. A ceric hydrocarbylsilyloxide according to claim 1 having one silicon atom in a singlesilyloxide group.
 3. A ceric hydrocarbyl silyloxide according to claim 2having one silicon atom in a single silyloxide group linked via twooxygens to one cerium atom.
 4. A ceric hydrocarbyl silyloxide accordingto claim 1 having two silicon atoms in tow silyloxide groups linked viaoxygen to one cerium.
 5. A ceric hydrocarbyl silyloxide according toclaim 1 having three silicon atoms in three silyloxide groups linked viaoxygen to one cerium.
 6. A ceric hydrocarbyl silyloxide according toclaim 1 having four silicon atoms in four silyloxide groups linked viaoxygen to one cerium.
 7. A ceric hydrocarbyl silyloxide according toclaim 1 having the formula ##STR20## wherein: OX₁, OX₂, OX₃ and OX₄ areselected from the group consisting of OR₁, NO₃ and (O)_(4-y) SiR_(y) ;and any of X₁ and X₂ and X₃ and X₄ in the formula can be taken togetheras SiR_(y) ;R is hydrogen or a hydrocarbyl group having from one toabout ten carbon atoms; y is 1, 2 or 3; R₁ is hydrocarbyl having fromone to about ten carbon atoms;provided: at least one of X₁, X₂, X₃ andX₄ is SiR_(y) ; at least one R is hydrocarbyl; and no more than one R ishydrogen.
 8. A ceric hydrocarbyl silyloxide according to claim 7 havingthe formula: ##STR21##
 9. A ceric hydrocarbyl silyloxide according toclaim 7 having the formula: ##STR22## wherein R₁ is hydrocarbyl havingfrom one to about ten carbon atoms.
 10. A ceric hydrocarbyl silyloxideaccording to claim 7 having the formula: ##STR23## wherein R₁ ishydrocarbyl having from one to about ten carbon atoms.
 11. A cerichydrocarbyl silyloxide according to claim 7 having the formula:##STR24## wherein R₁ is hydrocarbyl having from one to about ten carbonatoms.
 12. A ceric hydrocarbyl silyloxide according to claim 7 havingthe formula: ##STR25## wherein R₁ is hydrocarbyl having from one toabout ten carbon atoms.
 13. A ceric hydrocarbyl silyloxide according toclaim 7 having the formula: ##STR26## wherein R₁ is hydrocarbyl havingfrom one to about ten carbon atoms.
 14. A ceric hydrocarbyl silyloxideaccording to claim 7 having the formula: ##STR27##
 15. A cerichydrocarbyl silyloxide according to claim 7 having the formula:##STR28##
 16. A ceric hydrocarbyl silyloxide according to claim 7 havingthe formula: ##STR29## wherein: R is a hydrocarbyl group having from oneto about ten carbon atoms, and the R's attached to any silicon can bethe same or different; andn is the number of units in the formula, andranges from 2 to 100.